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Electronic landscape of the P-cluster of nitrogenase as revealed through many-electron quantum wavefunction simulations

Li, Zhendong and Guo, Sheng and Sun, Qiming and Chan, Garnet Kin-Lic (2019) Electronic landscape of the P-cluster of nitrogenase as revealed through many-electron quantum wavefunction simulations. Nature Chemistry, 11 (11). pp. 1026-1033. ISSN 1755-4330. doi:10.1038/s41557-019-0337-3.

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The electronic structure of the metal cofactors of nitrogenase is central to biological nitrogen fixation. However, the P-cluster and iron molybdenum cofactor, each containing eight metal ions, have long resisted detailed characterization of their low-lying electronic states. Through exhaustive many-electron wavefunction simulation, we report on the full low-energy landscape of the P-cluster in three biologically relevant oxidation states. We trace the origin of the low-lying spectrum to the underlying local atomic states and their global recoupling, and how the interplay between antiferromagnetism, delocalization, and spin frustration as the geometry changes upon oxidation gives rise to the structure of the electronic landscape. Our results support the narrative that many-electron wavefunction simulations stand to provide a resolution of the complicated cofactors in nitrogenase at the electronic level.

Item Type:Article
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URLURL TypeDescription ReadCube access Paper ItemCode ItemCode
Li, Zhendong0000-0002-0683-6293
Guo, Sheng0000-0002-1083-1882
Sun, Qiming0000-0003-0528-6186
Chan, Garnet Kin-Lic0000-0001-8009-6038
Alternate Title:The electronic landscape of the P-cluster of nitrogenase
Additional Information:© The Author(s), under exclusive licence to Springer Nature Limited 2019. Received 12 May 2019; Accepted 20 August 2019; Published 30 September 2019. Data availability: The authors declare that all the data that support the findings of this study are available in the paper and its Supplementary Information, and/or from the authors on reasonable request. Code availability: The spin-projected and spin-adapted DMRG codes used in this work are available from GitHub repositories ( and This work was supported by the US National Science Foundation through grant no. NSF-CHE 1665333. The BLOCK and PySCF codes used in the calculations were developed by additional support from the US National Science Foundation through grant no. NSF-SSI 1657286. G.K.-L.C. is a Simons Investigator in Physics. Author Contributions: Z.L. and G.K.-L.C. designed the study and wrote the manuscript. Z.L. performed the calculations. S.G. contributed to interfacing SP-MPS to SA-MPS used in the BLOCK code. Q.S. contributed to interfacing the PySCF code with COSMO. All authors contributed to the discussion of the results. The authors declare no competing interests.
Funding AgencyGrant Number
Simons FoundationUNSPECIFIED
Subject Keywords:Metalloproteins; Quantum chemistry
Issue or Number:11
Record Number:CaltechAUTHORS:20181203-110439947
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:91401
Deposited By: Tony Diaz
Deposited On:03 Dec 2018 19:30
Last Modified:16 Nov 2021 03:41

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